Colored reflex light reflector



June 5, 1951 J. c. TATUM l 2,555,715

COLORED REFLEX LIGHT REFLECTOR Filed Sept. 13, 1947 IN V EN TOR.

Patented June 5, 1951 COLORED REFLEX LIGHT REFLECTOR John C. Tatum, St. Paul, Minn., assignor to Minnesota Mining & Manufacturing Company, St. Paul, Minn., a corporation of Delaware Application September 13, 1947, Serial No. 773,840

5 Claims.

This invention relates to reflex light reilectors of the class having a catadioptric structure wherein a layer of minute transparent sphere lenses (glass beads) is partially embedded in a reective binder layer. Such reflectors have the property of directing a brilliant cone of light back toward the source of an angularly incident beam of light (see Fig. 1). Road signs and markers of the reflex type have greater visibility at night to the occupants of an approaching vehicle, since the reflected light is concentrated in a narrow cone which automatically returns toward lthe headlights and occupants of the vehicle.

The present invention provides a new and useful colored type of reflex reflector arrangement which has a novel combination of structural optical elements so related as to provide high-brilliancy wide-angularity reflection properties. The reflector emits colored light of high brilliancy even when the incident beam of light strikes the sphere layer at a large angle from the perpendicular (normal), as viewed by persons near the axis of the incident beam.

This invention is based upon the discovery of the reflection characteristics produced by a layer of minute transparent Spheres having a refractive index of approximately 1.9, when partially embedded in a reflective binder layer composed of 4a transparent film material containing a mixture'of nely divided aluminum flake pigment and transparent color pigment. The reflection is produced by the aluminum flakes and the lightcoloration is produced by particles of the .transparent color pigment acting as minute color filters.' The refractive index of the transparent color pigment is substantially equal to that of the transparent binder so as to minimize light-scattering and diffusion at the interfacial surfaces thereof. A refractive index of approximately 1.9 for the sphere lenses is needed to secure the desired color effect and this value also results in an optimum high-brilliancy wide-angularity characteristic. The correlation of variables will be subsequently discussed in more detail.

The reflector material can be fabricated in flexible, weatherproof, sheet form adapted for application to desired bases (including embossed sheet metal bases) in the making of highway signs and markers. The structure can also be built up by applying suitable coatings directly to a still base.

' The invention can best be described and explained in connection with the accompanying illustrative diagrammatic drawings, wherein:

Fig. l shows in diagram form a reflex reflector sheet lll and the concentrated cone of brilliant 1 reflex-reflected light returning toward the source of an angularly incident ray or beam. The action is quite different from that of a mirror which causes specular reflection, and from that of a reflective diffusing surface which causes the reflected light to spread out in all directions.

Fig. 2 is a highly magnified diagram View showing the sectional structure of a ilexible reflex reflector sheet embodying the invention. For greater clarity, the spheres are shown farther apart than the normal close-packed relation.

This illustrative sheet has a non-fibrous llm construction which is self-sustaining but is temporarily attached to a removable carrier sheet 2! upon which the coatings are built up, and

which can be peeled oil when desired. The film.

structure has a back size coating 22, which is cast upon the carrier sheet and facilitates stripping, and which provides a smooth surface upon which is coated the back reflector film 23. Upon this is coated the reflective binder layer 24 in which is partially embedded a single surface layer of minute transparent spheres 251, having a refractive index of approximately 1.9, which have been pressed in while the binder coating was still in a plastic condition (before curing) so that the back extremities touch or closely appreach the underlying back reflector film. This reflective binder layer, upon hardening, firmly holds the spheres in .position and contacts the rearward surfaces thereof.

The back reflector coating 23, and the reflective binder coating 24, serve to provide a novel type of colored reflective material contiguous to the back surfaces of the sphere lenses. The combination constitutes a chromatic catadioptric optical structure which refracts, filters and reilects in such a manner as to produce the colored reflex-reflecting action previously described.

These reflective coatings are composed of a clear transparent film-forming body material containing a mixture of finely divided aluminum flake pigment and transparent color pigment. The aluminum flakes of the back reflector coating 23 tend to lie fiat at the surface. The aluminum flakes of the binder coating 24, as a result of the entry of the spheres into this layer during the making operation, tend to beoriented so that they face toward the adjacent sphere surfaces.

proximity to the rearward hemispherical surface of each sphere lens, but spaced therefrom. The transparent color pigment particles are minutely small compared to the aluminum flakes, and some of these particles 11e scattered between each` The two coatings thus provide minute` flat silvery reflective surfaces facing and in close.

sphere surface and the adjacent flakes so as to 1 lter the light rays both before and after reiiection from the flakes. This filter action produces a color hue in the light rays transmitted through the particles, the degree of chroma (color intensity) depending upon the correlation of proportions.

Referring to Fig. 2, the light rays (a) represent substantially paraxial rays from a distant light source approaching the outer exposed face of a particular sphere in a direction normal to the plane of the reflector sheet. Owing to spherical and chromatic aberration effects, these incident rays cannot be brought to a true focus. But a sphere lens of refractive index approximating 1.9 will refract the rays so that they converge and strike the rear surface of the sphere within a small area zone, as shown. The rays proceed through the transparent material of the reflector Y (including the transparent color pigment part'icles) until reflected by the aluminum flakes, which occurs while the rays are closely focused andnear the sphere surface. The reiiected rays (except forl those which are scattered) lform a divergent cone of rays which are refracted at the front surface of the sphere so as to be concentrated in a narrow cone having substantially the same axisas the incident rays. The colored rays emitted from all of the spheres form a total cone of rays of limited divergency which proceeds toward the source of light. Persons located so that their lines of sight are close to the axis of the illuminating beam will see the reiiector sheet as a, brilliant colored area whose visibility far exceeds an .ordinary painted sheet. The minute size of the spheres prevents distinguishing them and the reflector sheet appears as though continuously Acoa'tedwith a brilliant .colored paint. Moreover, the combination of aluminum flakes and transparent. color pigment provides a luminous live color effect which creates an impression quiteA different from that of ordinary painted surfaces.

The paraxial Arays (b) are shown striking the outer surface of an exposed sphere at a substantial angle to the normal, with the result that the rays converge close to an axial point on the side under-surface of the sphere, and are reflected and colored by the binder layer. The colored reflected rays return toward the angularly positioned light source in the manner just described for normally incident rays. This accounts for the re'ex .reflection characteristic.

When-viewed by daylight, the reflector surface hasa continuous colored appearance of about the same hue, but 'the color is darker. Y

Thev nature of the invention will further appear from the description of the following illustrative specific example in connection with which a discussion will Ybe given of the results produced .by changing the proportions and other variables.

Example This example illustrates the making of a1 weather-proof, :lieXible and rstretchable lm type of reflex reiiec'tor sheeting of the kind shown in Fig. 2, adapted to be manufactured in continuous web VVform .and supplied .in rolls, 'which may be readily cut into sheets or shapes of desired configuration for affixing to base surfaces in the makingof signs 'and markers. All Aparts are by weight.

The carrier web is prepared from a highly calendere'd hard-surfaced paper (such as a '70 lbsper ream Fourdrinier paper) which is knifecoated with a 40% solution of isobutyl methacrylate polymer in xylol solvent in the amountV of about 13 to l-6 grains per 24 sq. in. (wet weight) followed by drying (15 minutes at 120 F. is suitable). This coating adheres tenaciously to the paper and provides a smooth casting surface for the subsequent coating operations.

The back size coating of the reiiector sheet is then cast in two steps. The dried paper is first knife-coated with a 10% solution of polyvinyl butyral polymer (for example, the XYNC or XYSG grade of Vinylite sold by Carbide 8a Carbon Chemicals Corp.) in ethylene-glycol mono- Vethyl-ether solvent, in the amount of about 20 grains per 24 sq. in. (wet weight), followed by oven drying (one hour at 140 F. is suitable). This provides a back surface which facilitates dry-stripping from the paper carrier web. The second step is to apply a coating solution containing 12.5% of the polyvinyl butyral polymer and 4.2% of tricresyl phosphate plasticizer in the same solvent, inthe amount of about 40 to 45 grains per 24 sq. in. (wet Weight), followed by oven drying (5 minutes each at 160, 220 and 300 F., successively, is suitable).

The back reflector coating is then cast, using a Wet coating weight of 12 to 14 grains per 24 sq. in. of the following formulation:

Solution of thermo-setting urea-formaldehyde resin in volatile solvent (50% solids) 61.5 Heavy blown castor oil (plasticizer) 30.8

Ethylene-glycol monoethyl-ether (solvent) 5.0 Blue phthalocyanine pigment '7.7 Aluminum pigment (40XD grade) 5.0

This reflector coating is dried and cured by heating in an oven for l0 minutes at 160 F., 15 minutes at 280 F., and l5 minutes at 235 F., successively.

The binder layer is then applied by knife-coating vthe same formulation, using a wet coating weight of 12 to 1'7 grains per 24 sq. in. A portion of the solvent is removed from the applied coating by heatingfor 3 minutes at 225 F. With the coating still .in an uncured and plastic condition, transparent glass beads of approximately 1.90 refractive index and of No. 11 size (average diameter 'of about 5 to 7 mils) are applied to form a single packed layer, the excess being removed, and are pressed into the binder by passing the coated sheet between a pair of squeeze rolls (one being steel yand the other rubber-covered). The beaded sheet is then given -a final oven cure of l0 minutes at 240 F., and 90 to 120 minutes atv 195-205 F. Any surplus beads adhering to the surface vcan be removed *by* passing the webv around a roller and subjecting the beaded surface to the action of a rotary brush and air blast. Each embedded bea'd is contacted by the binder to somewhat above its middle, providing a;

mechanical .socketing to increase firmness of anchorage.

The reflector sheet can be stripped from the paper' carrier web and the latter can be reused, the reector sheet being fully self-sustaining. Typical reflector films, made Vas described, have a' tensile strength of "I to 10` lbs. rper inch width and a stretch value (at rupture) of r20 to 30%.

When the illumination direction is at'angle of 40 to the normal, the reflex reflection brilliancy is a-s high as for normal (perpendicular) incidence, showing the excellent wide angularity.

characteristic.V The reflex-reflection (nighttime) appearance is light blue, and the daylight color is a deep'grey-blue. 1

WithfurtherV reference'to the above-mentioned formulation of the reective coatings (back "re-f flector and beadbinder), an example of a coinmercially available urea-formaldehyde resin solution is the No. 227-8grade of Beetle sold by American Cyanamid Co., which is a 50% by vweight solution of thermosetting urea-formaldehyderesin in a volatile solventcomposedwof 60 parts butyl alcohol and i parts xylol. Anexample of a blue phthalocyanine pigment is the Monastral Blue Toner BT172-D,"so ld by ELI'. du Pont de Nenfo-urs & Co.

The phthalocyanine pigments, toners and lakes, are insoluble and each serves as a pigment, in contradistinction to solublephthalocyanine dyes. This class of coloring agents is described in an article in Industrial and Engineering Chemistry, July, 1939, pages 839-847. The invention is not limited thereto. The use of transparent color pigments in printing inks is well known and various suitable pigments are available', including various lake-type pigments.-

The color pigment should be as light-fast as possible so as to minimize bleaching out of the color in reflectors subjected to continuous outdoor exposure. l

In making up the pigmented coating compositions,A the preferred procedure is to prepare a color pigment concentrate by milling the color pigment with suincient of `the castor oil to provi Labout-a 20% by weight concentration, thereby. separating and dispersing thev pigment particles. This pigment concentrate canothen be mixed in the proper ratio with the remaining ingredients to make up the ultimate formulation used for coating.

Taking the foregoing formulation of the reective coatings as a reference point, the effect of Variations will now be briefly indicated as follows:

In the above formulation the weight percent of the aluminum pigment relative to the total of resin solids plus castor oil (which provides the transparent film body of the dried coatings) is 8.13%. rlhe weight percent of the blue color pigment is 12.5%. Thus each type of pigment is present in the dried reflective coating in a plural percent proportion which is smaller than the proportion of the transparent iilm body material (by weight relative to the total of transparent nlm body material plus pigments) the proportion of aluminum ilake pigment on this basis being 6.7% and that of the transparent blue color pigment being 10.4%. Increasing the color pigment ratio deepens the color but decreases the reflex-reilection brilliancy value (as measured by a photo-electric cell). Decreasing the color pigment ratio increases brilliancy but weakens the color intensity (chroma). Increasing the aluminum pigment ratio increases the reflex-reflection brilliancy but weakens` the color, and vice versa. A further effect of variation is that the degree of divergency of the reflected rays is somewhat increased by decreasing the color pigment ratio or by increasing the aluminum pigment ratio. It is evident that a proper correlation of pigment ratios is required for the most desirable balance of visibility and color appearance properties. The optimum numerical value of the color pigment ratio depends of course upon the particular pigment being used, since pigments vary as to hue and as to absorption, depending both on the composition of the pigment and the particle size.

The 40XD grade of aluminum flake pigment mentioned in the formulation has a particle size of about 0.3 mil (i. e. the iiakes will pass through a screen opening having a breadth of approximately 0.0003 inch). This is far larger 'than the sizeof the 4color pigment particles, which are of colloidal size, but is much smaller than. the size of the glassbeads. The use of large aluminum flakes results in a decrease of refleX-reecti brilliancy and the color deepens, comparing equal weight percentages.

The `refractive index of theQQglaSsjbeads is a highly critical factor. The optin'iui'nl ,value iis close to1.90 Increasing the value to 1.95 defcreases brilliancy and greatly weakens the color effect. Decreasing the value to 1.85 deepens the color but considerably decreases thel brilliancy..-`

Considerable variation in bead size does not appreciably affect the optical properties within a size range (averagediameter) of about 3 to 10 "mils The use of thesey smallbeads provides a relatively smooth outer front surface (adapted to be painted or printed in` making signs) and permits of a very thin and pliable reflector sheetl The number of such beads per square inch of a single layer exceeds 10,000.

The expedient shown in Fig. 2 of using two separate reflective coatings (23 and 24) isA not essential tothe invention. The back reflector coating '23 can be omitted `without resulting'v in dead spots behind the spheres provided that-the spheres are embedded in the binder coating y'M so as not to penetrate to the' back surface thereof, thereby allowing. the backl extremities of the spheres to be adequately covered with the coating composition to provide reilection for normally incident rays. However, the illustrated expedient is advantageous for factory production as proper control is more easily secured.

It is also possible to employ the principle of the invention in other specific types of construction; For example, if back reflector coating 23 contains` aluminum pigment without the color pigment being present, the reflex-reflection appearance will be silvery for normally, incident light beams, but will have the colored appearance for angularly incident light due to the color pigment in the binder coating 24.

'I'he aluminum flake pigment is a preferred species of reflective metallic flake pigmentl but it will be understood that other species can be used as equivalents in keeping with the principles of the invention. For example, a yellow bronze flake pigment may be used in combination with a transparent yellow color pigment, in making a reflector having a clear yellow color. If aluminum flake pigment is used with transparent yellow color pigment a greenish cast is imparted to reflected light owing to the silvery reflection characteristic of aluminum.

It will be understood that each class of pigment may consist of a blend of two or more specifically different pigments. For example, a mixture of aluminum flake pigment and bronze flake pigment may be used as the metallic flake pigment constituent. Mixtures of transparent color pigments of differing hues may be used. The transparent lm body of the reflective layers may be tinted by a dye to modify the coloration, and tinted spheres may be used for the same purpose. Such combinations permit of additional variations in the color appearances of the reilex reflector.

Having described various embodiments of the invention, for purposes of illustration rather than limitation, what is claimed is as follows:

l. A reflex light reflector having a single layer of minute transparent spheres, whose refracama-'zat tive index is approximately 1.9, `partial-ly em bedded in a Areflective layer contacting the vinner surfaeesof the spheres, `forming a catadiopt-ric combination, said reeetive layer being formed of -a transparent body material adm-ixed with smaller but plural percent proportions (by Weight relative to the'total) of reflective metallic flake pigment and transparent coldr pigment, the metallic flakes being oriented in proximity to each embedded sphere surface so as to face toward i'tffand the proportions of the pigments being correlated, as herein described, so as to provide effectivecoloration and high brilliancy of reex-refleeted light.

2. A reflex light rellector according to claim 1, wherein the transparent color pigment is a lightfast phthalocyanine pigment.

3. A reex light reflector according to claim l, wherein vthe spheres are glass beads 'having an average `"diameter in the range of about 3 to l0 mils, and the metallic pigment consists of aluminum akes having a size of the order of 0.3 mil.

4, A reflex light rellector'sheet including aat back-f reflector layer, an overlying?'reflectiyele glassbeads partially embedded therein so asfto closely approach the back reflector, the"'glass` binder coating, and a single layer of transparent beads'having a refractive index close to '1.90 and an average diameter in the range of about f3 to 10 mils, said reflector layer and binder coating being each composed of a clear transparent lm material intimately admixed with smaller but plural percent propontions (by weight relativ-e to the total) of reective metallic flake pigment and transparent color pigment, the metallic flakes being oriented in proximity to each embedded -sphere surface so as to face toward it, and `the proportions Aof the pigments being ycor.- related, as herein described, so as to provide eiec, tive coloration and high brilliancy of reexfreflectedv light lboth for normally and angularly incident light beams.

5. A reflex light` reector sheet according to claim 4, Whe-rein the metallic pigment consists of aluminum ilakes having a size of the order of 0.3 mil and the transparent color pigment is a lightfast phthalocyanine pigment.

JOHN C. TATUM.

20 file of this patent:

I UNITED STATES PATENTS Number Name Date 2,302,305 Farrell Nov. 17, 1942 2,326,634 Gebhard et al Aug. l0, 1943 2,354,049 Palmqu-ist July 18, 1944 2,379,702 `Gebhard July 3, 1945 2,379,741V Palmquist July 3, 1945 2,383,884 Palmquist Aug. 28, 1945 2,407,680 Palmcluist et al. Sept. 17, 1946 2,440,584 Heltzer et al. Apr. 27, 194-8 

1. A REFLEX IS LIGHT REFLECTOR HAVING A SINGLE LAYER OF MINUTE TRANSPARENT SPACES, WHOSE REFRACTIVE INDEX IS APPROXIMATELY 1.9. PARTIALLY EMBEDDED IN A REFLECTIVE LAYER CONTACTING THE INNER SURFACES OF THE SPHERES, FORMING A CATADIPTRIC COMBINATION, SAID REFLECTIVE LAYER BEING FORMED OF A TRANSPARENT FILM BODY MATERIAL ADMIXED WITH SMALLER BUT PLURAL PERCENT PROPORTIONS (BY WEIGHT RELATIVE TO THE TOTAL) OF REFLECTIVE METALLIC FLAKE PIGMENT AND TRANSPARENT COLOR PIGMENT, THE METALLIC FLAKES BEING ORIENTED IN PROXIMITY TO EACH EMBEDDED SPHERE SURFACE SO AS TO FACE TOWARD IT, AND THE PROPORTIONS OF THE PIGMENTS BEING CORRELATED, AS HEREIN DESCRIBED, SO AS TO PROVIDE-EFFECTIVE COLORATION AND HIGH BRILLIANCY OF REFLEX-RELFECTED LIGHT. 